JPWO2016190366A1 - Water / oil repellent composition, method for producing the same, and article - Google Patents

Abstract

Water / oil repellent composition capable of obtaining an article having good water repellency, oil repellency, washing durability, heavy rain durability and texture, its production method, and water repellency, oil repellency, washing durability, Provided is an article having good heavy rain durability and texture. A water / oil repellent composition comprising a copolymer having a unit based on the monomer (a), a unit based on the monomer (b) and a unit based on the monomer (c), and a liquid medium. Monomer (a): (ZY) nX (Z: perfluoroalkyl group having 1 to 6 carbon atoms, Y: divalent organic group, etc., n: 1 or 2, X: polymerizable unsaturated group) A compound represented by Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 or more carbon atoms. Monomer (c): a compound represented by CH2 = CR1C (O) O-[(C2H4O) a (C4H8O) b] -H (R1: a hydrogen atom or a methyl group, a / b = 1 to 3).

Description

  The present invention relates to a water / oil repellent composition, a method for producing the same, and an article treated with the water / oil repellent composition.

  As a method for imparting water / oil repellency to the surface of an article (textile product, etc.), a water / oil repellent composition in which a copolymer having a unit based on a monomer having a polyfluoroalkyl group is dispersed in a liquid medium. There is known a method of processing an article by using the above. Articles treated with the water / oil repellent composition have no significant decrease in water repellency even after repeated washing (washing durability), and greatly decrease in water repellency even when exposed to heavy rain conditions. Not to do (torrential rain durability) is required.

As the water / oil repellent composition having excellent washing durability and heavy rain durability, for example, the following water / oil repellent composition has been proposed.
(1) A water / oil repellent composition comprising a copolymer having units based on the following monomer 1 and units based on the following monomer 2 (Patent Document 1).
Monomer 1: (meth) acrylate having a perfluoroalkyl group having 1 to 6 carbon atoms.
Monomer 2: (meth) acrylate having an alkyl group having 20 to 30 carbon atoms.

As the water and oil repellent composition having excellent antifouling properties and washing durability, for example, the following antifouling agent compositions have been proposed.
(2) An antifouling agent composition comprising a copolymer having a unit based on the following monomer 3, a unit based on the following monomer 4 and a unit based on the following monomer 5 (Patent Document 2).
Monomer 3: (meth) acrylate having a perfluoroalkyl group having 1 to 6 carbon atoms.
Monomer 4: (meth) acrylate having a poly (oxyethylene) chain.
Monomer 5: (meth) acrylate having a poly (oxyethylene / oxytetramethylene) chain.

(3) Copolymer having a unit based on the following monomer 6, a unit based on the following monomer 7 and a unit based on the following monomer 8 and a proportion of fluorine atoms of 15% by mass or more and less than 45% by mass Coalescence,
A copolymer having a unit based on the following monomer 6, a unit based on the following monomer 7 and a unit based on the following monomer 8 and a proportion of fluorine atoms of 45% by mass or more;
An antifouling agent composition comprising a unit based on the following monomer 6, a unit based on the following monomer 9, and a copolymer having a unit based on the following monomer 10 (Patent Document 3).
Monomer 6: (meth) acrylate having a polyfluoroalkyl group having 4 to 6 carbon atoms.
Monomer 7: (meth) acrylate having an alkyl group having 12 or more carbon atoms.
Monomer 8: Vinyl chloride or vinylidene chloride.
Monomer 9: (meth) acrylate having a poly (oxyethylene) chain.
Monomer 10: (meth) acrylate having a poly (oxyethylene / oxytetramethylene) chain.

International Publication No. 2008/136436 International Publication No. 2008/143299 JP 2009-215370 A

However, the article treated with the water / oil repellent composition (1) has insufficient oil repellency.
Articles treated with the water / oil repellent composition (2) have insufficient washing durability and texture.
Articles treated with the water / oil repellent composition (3) have insufficient washing durability and texture.

  The present invention provides a water / oil repellent composition, a method for producing a water / oil repellent composition capable of obtaining an article having good water repellency, oil repellency, washing durability, heavy rain durability and texture, and Provided is an article having good water repellency, oil repellency, washing durability, heavy rain durability and texture.

The present invention has the following aspects.
[1] Water and water repellency comprising a copolymer having a unit based on the following monomer (a), a unit based on the following monomer (b), and a unit based on the following monomer (c) and a liquid medium Oil composition.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, the group represented by the following Formula (2-1), or the group represented by the following Formula (2-2), Y is fluorine It is a divalent organic group or a single bond having no atom, n is 1 or 2, and X is represented by the following formulas (3-1) to (3-5) when n is 1. Any one of the groups, and when n is 2, any one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C s F 2s + 1 (CH} 2 CF 2) t (CF 2 CF 2) u - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, s is an integer from 1 to 6 T is an integer of 1 to 4, and u is an integer of 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 or more carbon atoms.
Monomer (c): a compound represented by the following formula (5).
^{_{CH 2 = CR 1 C (O}} ) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ··· (5).
However, ^{R 1} is hydrogen atom or a methyl group, a is 3 to 50, b is 1 to 50, the ratio between a and b (a / b) is a 1-3 . Further, the bonding order of the (C ₂ H ₄ O) unit and the (C ₄ H ₈ O) unit is not limited.

[2] The content ratio of the units based on the monomer (a) is 5 to 40% by mass with respect to the units based on all monomers constituting the copolymer, and the monomer (b ) Based unit content is 40 to 94.9% by mass, and the unit content based on the monomer (c) is 0.1 to 20% by mass. Composition.
[3] The water / oil repellent composition according to [1] or [2], wherein the copolymer further has a unit based on the following monomer (d).
Monomer (d): Halogenated olefin.
[4] The water / oil repellent composition according to [3], wherein the monomer (d) is vinyl chloride.
[5] The ratio of the unit based on the monomer (d) is 30% by mass or less with respect to the units based on all monomers constituting the copolymer, according to [3] or [4] Water / oil repellent composition.
[6] The water / oil repellent composition according to any one of [1] to [5], wherein the copolymer further has units based on the following monomer (e).
Monomer (e): A monomer having a functional group capable of crosslinking.
[7] The water / oil repellent composition according to any one of [1] to [6], wherein the liquid medium is an aqueous medium.

[8] A monomer component containing the following monomer (a), the following monomer (b), and the following monomer (c) in a liquid medium in the presence of a surfactant and a polymerization initiator. A method for producing a water / oil repellent composition, which is polymerized into a copolymer.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, the group represented by the following Formula (2-1), or the group represented by the following Formula (2-2), Y is fluorine It is a divalent organic group or a single bond having no atom, n is 1 or 2, and X is represented by the following formulas (3-1) to (3-5) when n is 1. Any one of the groups, and when n is 2, any one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C s F 2s + 1 (CH} 2 CF 2) t (CF 2 CF 2) u - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, s is an integer from 1 to 6 T is an integer of 1 to 4, and u is an integer of 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 or more carbon atoms.
Monomer (c): a compound represented by the following formula (5).
^{_{CH 2 = CR 1 C (O}} ) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ··· (5).
However, ^{R 1} is hydrogen atom or a methyl group, a is 3 to 50, b is 1 to 50, the ratio between a and b (a / b) is a 1-3 . _The binding order of the (C _{2 H} 4 O) units and _{(C 4 H} 8 O) units is not limited.

[9] The ratio of the monomer (a) is 5 to 40% by mass and the ratio of the monomer (b) is 40 to 94.9% by mass with respect to the total amount of the monomer components. The method for producing a water / oil repellent composition according to [8], wherein the ratio of the monomer (c) is 0.1 to 20% by mass.
[10] The method for producing a water / oil repellent composition according to [8] or [9], wherein the monomer component further comprises the following monomer (d).
Monomer (d): Halogenated olefin.
[11] The method for producing a water / oil repellent composition according to any one of [8] to [10], wherein the monomer component further comprises the following monomer (e).
Monomer (e): A monomer having a functional group capable of crosslinking.
[12] The method for producing a water / oil repellent composition according to any one of [8] to [11], wherein the liquid medium is an aqueous medium.

[13] An article treated with the water / oil repellent composition according to any one of [1] to [7].
[14] The article according to [13], wherein the article is a textile product.

According to the water / oil repellent composition of the present invention, an article having good water repellency, oil repellency, washing durability, heavy rain durability and texture can be obtained.
According to the method for producing a water / oil repellent composition of the present invention, a water / oil repellent composition capable of obtaining an article having good water repellency, oil repellency, washing durability, heavy rain durability and texture. Can be manufactured.
The article of the present invention has good water repellency, oil repellency, washing durability, heavy rain durability and texture.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
In the present specification, a group represented by the formula (2) is referred to as a group (2). Groups represented by other formulas are also described in the same manner.
The meanings of the following terms in this specification are as follows.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“Monomer” means a compound having a polymerizable unsaturated group.
The “polyfluoroalkyl group” means a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Hereinafter, “polyfluoroalkyl group” is also referred to as “R ^f group”.
“Perfluoroalkyl group” means a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms. Hereinafter, a "perfluoroalkyl group" is also referred to as "R ^F group".
The “number average molecular weight” and “mass average molecular weight” of the copolymer are values determined in terms of polystyrene by gel permeation chromatography (GPC).
“A” and “b” of the [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] chain of the monomer (c) are the average number of units of oxyethylene units and oxytetramethylene units, respectively. Yes, a value calculated by nuclear magnetic resonance spectroscopy (NMR).
The “number average molecular weight” of the [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] chain of the monomer (c) is obtained by multiplying the molecular weight of the oxyethylene unit by the average number of units, It is a value obtained by adding the value obtained by multiplying the molecular weight of the tetramethylene unit by the average number of units.

<Water / oil repellent composition>
The water / oil repellent composition of the present invention contains a specific copolymer and a liquid medium as essential components, and optionally contains a surfactant and an additive.

(Copolymer)
The copolymer has a unit based on the monomer (a), a unit based on the monomer (b), and a unit based on the monomer (c).
The copolymer preferably further has units based on the monomer (d) and / or units based on the monomer (e).
The copolymer may have a unit based on the monomer (f) as necessary.

Monomer (a):
Monomer (a) is compound (1).
(ZY) _n X (1).

Z is a C 1-6 R ^F group, a group represented by the following formula (2-1), or a group represented by the following formula (2-2).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C s F 2s + 1 (CH} 2 CF 2) t (CF 2 CF 2) u - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, s is an integer from 1 to 6 T is an integer of 1 to 4, and u is an integer of 1 to 3.
The number of carbon atoms of the R ^F group is 4-6 are preferable. The ^RF group may be linear or branched, and is preferably linear.
Examples of Z include F (CF ₂ ) ₄ —, F (CF ₂ ) ₅ —, F (CF ₂ ) ₆ —, (CF ₃ ) ₂ CF (CF ₂ ) ₂ — and the like.

Y is a divalent organic group having no fluorine atom or a single bond.
As the divalent organic group, an alkylene group is preferable. The alkylene group may be linear or branched. The alkylene group is —O—, —NH—, —CO—, —SO ₂ —, —S—, —CD ¹ ═CD ² — (wherein D ¹ and D ² are a hydrogen atom or a methyl group, respectively. ), -Φ-OCO-, and the like.
The _{Y, -CH 2 -, - CH} 2 CH 2 -, - (CH 2) 3 -, - CH 2 CH 2 CH (CH 3) -, - CH = CH-CH 2 -, - S-CH 2 _{CH 2 -, - SO 2 -CH} 2 CH 2 -, - CH 2 CH 2 CH 2 -S-CH 2 CH 2 -, - CH 2 CH 2 CH 2 -SO 2 -CH 2 CH 2 -, - φ- _{OCO-CH 2 CH} 2 - and the like.

n is 1 or 2.
X is any one of groups (3-1) to (3-5) when n is 1, and when n is 2, X is any of groups (4-1) to (4-4). Either.

-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

Examples of the compound (1) include polymerizability with other monomers, copolymer film flexibility, adhesion of the copolymer to the article, dispersibility or solubility in the liquid medium, and ease of emulsion polymerization. From the above point, an acrylate having 1 to 6 carbon atoms, an acrylate having an R 3 ^F group, an acrylate substituted with a halogen atom at the α-position, or an acrylate or methacrylate having a group (2-2) is preferable, and the number of carbon atoms is 4 acrylate having 6 to R ^F group, methacrylate or α-position acrylates substituted with a halogen atom is more preferable.
As the compound (1), Z is an ^{R F} group having 4 to 6 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, n is 1, X is a group (3-3) , R is particularly preferably a hydrogen atom, a methyl group or a chlorine atom.
Preferred examples of the compound (1) _{is, C 6 F 13 C 2 H} 4 OCOC (CH 3) = CH 2, C 6 F 13 C 2 H 4 OCOCH = CH 2, C 6 F 13 C 2 H 4 OCOCCl _{= CH 2, C 4 F 9} C 2 H 4 OCOC (CH 3) = CH 2, C 4 F 9 C 2 H 4 OCOCH = CH 2, C 4 F 9 C 2 H 4 OCOCCl = CH 2, C 4 F _{9 CH 2 CF 2 C 4 F} 8 C 2 H 4 OCOCH = CH 2, C 4 F 9 CH 2 CF 2 C 4 F 8 C 2 H 4 OCOC (CH 3) = CH 2, C 6 F 13 C 2 H ₄ OCOφOCOCH═CH ₂ , C ₄ F ₈ C ₂ H ₄ OCOφOCOCH═CH ₂ .

Monomer (b):
The monomer (b) is a (meth) acrylate having no R ^f group and having an alkyl group having 20 or more carbon atoms. 20-30 are preferable and, as for carbon number of an alkyl group, 20-24 are more preferable.
If the carbon number of the alkyl group is at least the lower limit, the washing durability and heavy rain durability of the article treated with the water / oil repellent composition will be good. When the number of carbon atoms of the alkyl group is not more than the above upper limit, handling in the polymerization operation is easy, and a copolymer can be obtained with good yield.
As the monomer (b), behenyl (meth) acrylate and icosyl (meth) acrylate are preferable, and behenyl acrylate is particularly preferable.

Monomer (c):
The monomer (c) is the compound (5).
^{_{CH 2 = CR 1 C (O}} ) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ··· (5).

R ¹ is a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of further improving the oil repellency of an article treated with the water / oil repellent composition.

a is 3-50, and 3-20 are more preferable. If a is at least the lower limit of the above range, the oil repellency of the article treated with the water / oil repellent composition will be good. If a is below the upper limit of the said range, the water repellency of the articles | goods processed using the water / oil repellent composition will become favorable.
b is 1-50, and 2-20 are more preferable. If b is at least the lower limit of the above range, the water repellency of the article treated with the water / oil repellent composition will be good. If b is below the upper limit of the said range, the oil repellency of the articles | goods processed using the water / oil repellent composition will become favorable.
The ratio (a / b) between a and b is 1 to 3, and more preferably 1.5 to 2.5. When a / b is at least the lower limit of the above range, the oil repellency of the article treated with the water / oil repellent composition will be good. If a / b is not more than the upper limit of the above range, the water repellency of the article treated with the water / oil repellent composition will be good.

The number average molecular weight of [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] is preferably 200 to 6000, and more preferably 300 to 2000. If the number average molecular weight of [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] is not less than the lower limit of the above range, the oil repellency of the article treated with the water / oil repellent composition is improved. Even better. If the number average molecular weight of [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] is less than or equal to the upper limit of the above range, the water repellency of the article treated with the water / oil repellent composition is improved. Even better.

In [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ], the bonding order of a mole of (C ₂ H ₄ O) unit and b mole of (C ₄ H ₈ O) unit is not limited. . For example, (C ₂ H ₄ O) units and (C ₄ H ₈ O) units may be randomly arranged, and (C ₂ H ₄ O) units and (C ₄ H ₈ O) units are alternately arranged. Alternatively, a block composed of a plurality of (C ₂ H ₄ O) units and a block composed of a plurality of (C ₄ H ₈ O) units may be connected. The (C ₂ H ₄ O) unit and the (C ₄ H ₈ O) unit may be randomly arranged from the point that the oil repellency of the article treated with the water / oil repellent composition is further improved. preferable.
The (C ₂ H ₄ O) unit and the (C ₄ H ₈ O) unit may be linear or branched. From the viewpoint that the effects of the present invention can be sufficiently exerted, a straight chain is preferable.

When the copolymer has units based on the monomer (c), oil repellency, washing durability and heavy rain durability can be sufficiently exhibited.
This is because the monomer having a (C ₂ H ₄ O) unit and a (C ₄ H ₈ O) unit has a glass transition temperature of a homopolymer rather than a monomer having only a (C ₂ H ₄ O) unit. As a result, the glass transition temperature of the copolymer having a unit derived from a monomer having a (C ₂ H ₄ O) unit and a (C ₄ H ₈ O) unit is lowered, and the film forming property is improved. It is considered that the adhesion to the base material is improved. In addition, since the monomer having (C ₂ H ₄ O) and (C ₄ H ₈ O) is hydrophobic, it is also oleophobic, so that the water repellency and oil repellency of the copolymer must be inhibited as a result. Conceivable.

Monomer (d):
The monomer (d) is a halogenated olefin.
By combining the unit based on the monomer (b) and the unit based on the monomer (d), the adhesion to the article is improved, so that washing of the article treated with the water / oil repellent composition is performed. Durability and heavy rain durability are further improved.

Examples of the halogenated olefin include compounds represented by the following formula (6).
R ⁴ R ⁵ C = CR ⁶ R ⁷ (6)
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or a C ¹ to C 3 perfluoroalkyl group. However, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is a halogen atom or a C 1 to C 3 perfluoroalkyl group. The perfluoroalkyl _{group, CF 3 -, C 2 F} 5 -, C 3 F 7 - a.
As the halogenated olefin, a chlorinated olefin and a fluorinated olefin are preferable.

As the halogenated olefin, tetrafluoroethylene or a compound represented by the following formula (7) is preferable.
R ⁸ HC = CR ⁹ R ¹⁰ (7)
R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a chlorine atom, a fluorine atom, or a C ¹ to C 3 perfluoroalkyl group. Provided ^that at least one of R ^8, R ^{9, R 10} is a chlorine atom, a fluorine atom or perfluoroalkyl group having 1 to 3 carbon atoms.
Specific examples of the halogenated olefin include vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride, 2,3,3,3-tetrafluoro-1-propene, 1-chloro-3,3,3-trifluoro Propene (E form), 1-chloro-3,3,3-trifluoropropene (Z form), trifluoroethylene, 1,2-difluoroethylene (E form), 1,2-difluoroethylene (Z form), Examples include 1-chloro-2,3,3,3-tetrafluoro-1-propene (E-form), 1-chloro-2,3,3,3-tetrafluoro-1-propene (Z-form) and the like. Among these, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylidene fluoride, and 2,3,3,3-tetrafluoro-1-propene are preferable, and vinyl chloride, vinylidene chloride, 2,3,3,3-tetrafluoro-1-propene is more preferred.

Monomer (e):
The monomer (e) is a monomer having a functional group capable of crosslinking (except for the monomer (c)).
When the copolymer has units based on the monomer (e), the durability (washing durability and heavy rain durability) of the article treated with the water / oil repellent composition is further improved.

The functional group capable of crosslinking is preferably a functional group having at least one bond among a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a crosslinked structure by the interaction of the bonds.
The functional group includes isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, alkoxymethylamide group, silanol group, ammonium group, amide group, epoxy group, hydroxyl group, oxazoline group, carboxyl group, alkenyl group, sulfone. Acid groups and the like are preferable. In particular, an epoxy group, a hydroxyl group, a blocked isocyanate group, an alkoxysilyl group, an amino group, or a carboxyl group is preferable.

As the monomer (e), (meth) acrylates, acrylamides, vinyl ethers, or vinyl esters are preferable.
As the monomer (e), N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-isocyanatoethyl ( 3,5-dimethylpyrazole adduct of (meth) acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, diacetone acrylamide, glycidyl methacrylate, glycerol (meth) acrylate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, polycaprolactone ester of hydroxyethyl (meth) acrylate, phenylglycidylethyl acrylate tolylene diisocyanate (AT-600, manufactured by Kyoeisha Chemical Co., Ltd.) or 3- (methyl ester Ruketookishimu) isocyanatomethyl-3,5,5-trimethylcyclohexyl (2-hydroxyethylmethacrylate) cyanate (TEC coating HE-6P, Kyokinu Kasei Co., Ltd.) is more preferred.
As the monomer (e), N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate 3,5-dimethyl A pyrazole adduct, or a 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, or 3-chloro-2-hydroxypropyl (meth) acrylate is particularly preferable.

Monomer (f):
The monomer (f) is a monomer excluding the monomer (a), the monomer (b), the monomer (c), the monomer (d), and the monomer (e).

As the monomer (f), the following compounds may be mentioned.
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl methacrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (Meth) acrylate, vinyl acetate, vinyl propionate, butene, isoprene, butadiene, ethylene, propylene, vinylethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexyl Ethylene, neopentylethylene, (1,2-diethoxycarbonyl) ethylene, (1,2-dipropoxycarbonyl) ethylene, Kishiechiren, ethoxy ethylene, butoxy ethylene, 2-methoxy propylene, pentyl polyoxyethylene, cycloalkyl pentanoyloxy ethylene, cyclopentyl acetoxystyrene ethylene, styrene, alpha-methyl styrene, p- methyl styrene, hexyl styrene, octyl styrene, nonyl styrene, chloroprene.

  N, N-dimethyl (meth) acrylamide, vinyl alkyl ether, vinyl alkyl ketone, butyl acrylate, propyl methacrylate, benzyl (meth) acrylate, octyl (meth) acrylate, decyl methacrylate, cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy -Butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate, aziridinylethyl (meth) acrylate, 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyethylene glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate.

  Crotonic acid alkyl ester, maleic acid alkyl ester, fumaric acid alkyl ester, citraconic acid alkyl ester, mesaconic acid alkyl ester, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, silicone on side chain (Meth) acrylate having a urethane bond, (meth) acrylate having a polyoxyalkylene chain whose terminal is an alkyl group having 1 to 4 carbon atoms, alkylene di (meth) acrylate, and the like.

From the viewpoint of water and oil repellency, the copolymer has a monomer having only a (C ₂ H ₄ O) unit as a unit constituting a poly (oxyalkylene) chain, and has only a (C ₃ H ₆ O) unit. It is preferred not to have monomers or units based on monomers having only (C ₂ H ₄ O) units and (C ₃ H ₆ O) units.
Monomers having only (C ₂ H ₄ O) units, monomers having only (C ₃ H ₆ O) units, or (C ₂ H ₄ O) units and (C ₃ H ₆ O) units only When it has a unit based on the monomer it has, it is preferably added in a range that does not reduce the water and oil repellency of the copolymer. It is preferable that it is 0.1-3 mass% with respect to the unit based on all the monomers which comprise a copolymer.

The ratio of the units based on the monomer (a) is the ratio of all the monomers constituting the copolymer from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. 5-40 mass% is preferable with respect to the unit based, and 10-25 mass% is more preferable.
The proportion of the units based on the monomer (b) is based on all the monomers constituting the copolymer from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. 40-94.9 mass% is preferable with respect to the unit based, 40-91.9 mass% is more preferable, 40-91.8 mass% is further more preferable, 40-89.9 mass% is especially preferable, 40 -84.9% by mass is most preferred.
The proportion of the units based on the monomer (c) is the proportion of all monomers constituting the copolymer from the viewpoint of water / oil repellency and durability of the article treated with the water / oil repellent composition. 0.1-20 mass% is preferable with respect to the unit based, and 0.1-10 mass% is more preferable.
The proportion of the units based on the monomer (d) is the ratio of all monomers constituting the copolymer from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. 0-30 mass% is preferable with respect to the unit based, and 3-25 mass% is more preferable.
The proportion of the units based on the monomer (e) is based on the water / oil repellency and durability of the article treated with the water / oil repellent composition, to all the monomers constituting the copolymer. 0-20 mass% is preferable with respect to the unit based, and 0.1-10 mass% is more preferable.
The proportion of the units based on the monomer (f) is the ratio of all monomers constituting the copolymer from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. 0-35 mass% is preferable with respect to the unit based, and 0-20 mass% is more preferable.
The ratio of the units based on the monomer in the present invention is calculated based on the charged amount of the monomer at the time of producing the copolymer.

The weight average molecular weight (Mw) of the copolymer is preferably 8,000 to 1,000,000, and more preferably 10,000 to 800,000. When the weight average molecular weight (Mw) of the copolymer is within the above range, both water repellency and oil repellency can be expressed.
The number average molecular weight (Mn) of the copolymer is preferably 3000 to 800000, more preferably 5000 to 600000. If the number average molecular weight (Mn) of the copolymer is within the above range, both water repellency and oil repellency can be expressed.

(Liquid medium)
Examples of the liquid medium include water, alcohol, glycol, glycol ether, glycol ester, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent, organic acid, etc. An aqueous medium is preferable from the viewpoint of ease.
An aqueous medium means water, a water-soluble organic solvent, and those mixed media. As the water-soluble organic solvent, one or more water-soluble organic solvents selected from the group consisting of water-soluble monoalcohols, water-soluble glycols, water-soluble glycol ethers, and water-soluble glycol esters are preferable.

A liquid medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In the case of using a mixture of two or more liquid media, it is preferable to use a mixture of water and a water-soluble organic solvent. By using an aqueous medium in which water and a water-soluble organic solvent are mixed, it is easy to control the solubility and dispersibility of the copolymer, and control of the permeability, wettability, solvent drying speed, etc. to the article during processing is possible. It's easy to do.
The aqueous medium in the water / oil repellent composition of the present invention is preferably an aqueous medium containing water alone or an aqueous medium containing water and the water-soluble organic solvent. The amount of the water-soluble organic solvent in the water / oil repellent composition of the present invention is preferably 0 to 40% by mass, preferably 1 to 20% by mass, when the composition contains 20% by mass of the copolymer. Is more preferable.

(Surfactant)
Examples of the surfactant include a hydrocarbon-based surfactant and a fluorine-based surfactant, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, respectively. .
As the surfactant, a combination of a nonionic surfactant and an amphoteric surfactant is preferable from the viewpoint of compatibility with the additive, and from the viewpoint of the stability of the copolymer, the nonionic surfactant is preferably used. Use alone or a combination of a nonionic surfactant and a cationic surfactant is preferred.
The ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 97/3 to 40/60 (mass ratio).

Examples of the nonionic surfactant include surfactants s ^{1 to} s ⁶ described in International Publication No. 2010/047258 and International Publication No. 2010/123042, and an amidoamine interface described in Japanese Patent No. 5569614. One or more selected from activators are preferred.
When the surfactant contains a cationic surfactant, the surfactant s ⁷ described in International Publication No. 2010/047258 and International Publication No. 2010/123042 is preferable as the cationic surfactant.
When the surfactant contains an amphoteric surfactant, the amphoteric surfactant, WO 2010/047258, surfactant ^{s 8} as described in WO 2010/123042 preferred.
Further, as the surfactant, WO 2010/047258, it may be used WO 2010/123042 surfactants described in JP ^{s 9} (polymeric surfactant).
The preferable aspect of surfactant is the same as the preferable aspect described in international publication 2010/047258 and international publication 2010/123042.

Preferable specific examples of the nonionic surfactant include the following compounds.
_{C 18 H 37 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 30 H,
_{C 18 H 35 O- (CH 2} CH 2 O) 26 H,
_{C 18 H 35 O- (CH 2} CH 2 O) 30 H,
_{C 16 H 33 O [CH 2} CH (CH 3) O] 5 - (CH 2 CH 2 O) 20 H,
_{C 12 H 25 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{(C 8 H 17) (C} 6 H 13) CHO- (CH 2 CH 2 O) 15 H,
_{C 10 H 21 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O- (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 4 F 9 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H.
_{HO- (CH 2 CH 2 O)} 15 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 15 H,
_{HO- (CH 2 CH 2 O)} 8 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 8 H,
_{HO- (CH 2 CH 2 O)} 9 - (C 3 H 6 O) 20 - (CH 2 CH 2 O) 9 H,
HO— (CH ₂ CH ₂ O) ₄₅ — (C ₃ H ₆ O) ₁₇ — (CH ₂ CH ₂ O) ₄₅ H,
_{HO- (CH 2 CH 2 O)} 34 - (CH 2 CH 2 CH 2 CH 2 O) 28 - (CH 2 CH 2 O) 34 H.
_{CH 3 (CH 2) m -CH} [O (CH 2 CH 2 O) s H] - (CH 2) n CH 3
However, m + n represents an integer of 9 to 11, and s represents an integer of 3 to 15.

Preferred examples of the cationic surfactant include stearyl trimethyl ammonium chloride, stearyl dimethyl monoethyl ammonium ethyl sulfate, stearyl monomethyl di (polyethylene glycol) ammonium chloride, fluorohexyl trimethyl ammonium chloride, di (tallow alkyl) dimethyl ammonium chloride. Dimethyl monococonut amine acetate, amidoamine quaternary ammonium salts described in Japanese Patent No. 5569614, and the like.
Preferable specific examples of the amphoteric surfactant include dodecyl betaine, stearyl betaine, dodecylcarboxymethylhydroxyethylimidazolinium betaine, dodecyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine and the like.

  1-10 mass parts is preferable with respect to 100 mass parts of copolymers, and, as for the total amount of surfactant, 2-8 mass parts is more preferable.

(Additive)
Additives include penetrants, antifoaming agents (silicone antifoaming agents, etc.), water absorbing agents, antistatic agents, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol) Etc.), thermosetting agents (melamine curing agents such as methylol melamine, isocyanate curing agents such as blocked polyisocyanates), epoxy curing agents (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.) , Carbodiimide group-containing curing agent, oxazoline group-containing curing agent, thermosetting catalyst, crosslinking catalyst, synthetic resin, fiber stabilizer Triethanolamine, acetic acid, colloidal silica, and the like.

(Method for producing water / oil repellent composition)
In the method for producing the water / oil repellent composition of the present invention, the monomer (a), the monomer (b) and the monomer are prepared in a liquid medium in the presence of a surfactant and a polymerization initiator. In this method, a monomer component containing (c) is polymerized to form a copolymer. Further, as the monomer component, one or more of the monomer (d), the monomer (e) and the monomer (f) can be used.
The water / oil repellent composition of the present invention can be produced, for example, by the following method (i) or (ii).
(I) A monomer component containing monomers (a) to (c) and, if necessary, monomers (d) to (f) in a liquid medium in the presence of a surfactant and a polymerization initiator Is obtained by polymerizing the copolymer to obtain a solution, dispersion or emulsion of the copolymer, and then adding a liquid medium, a surfactant or an additive as necessary.
(Ii) A monomer component containing monomers (a) to (c) and, if necessary, monomers (d) to (f) in a liquid medium in the presence of a surfactant and a polymerization initiator Is obtained by polymerizing the copolymer to obtain a solution, dispersion or emulsion of the copolymer, and then separating the copolymer, and adding a liquid medium, a surfactant and, if necessary, an additive to the copolymer.
Examples of the polymerization method include a dispersion polymerization method, an emulsion polymerization method, and a suspension polymerization method.

As a method for producing a water / oil repellent composition, monomers (a) to (c), and if necessary, monomers (d) to (()) in an aqueous medium in the presence of a surfactant and a polymerization initiator. A method of obtaining a copolymer emulsion by emulsion polymerization of the monomer component containing f) is preferred.
From the viewpoint of improving the yield of the copolymer, it is preferable to pre-emulsify a mixture comprising a monomer, a surfactant and an aqueous medium before emulsion polymerization. For example, a mixture comprising a monomer, a surfactant and an aqueous medium is mixed and dispersed with a homomixer or a high-pressure emulsifier. Further, the gaseous monomer can be added to an emulsified mixture obtained by pre-emulsification and copolymerized with the monomer in the emulsified mixture.

Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a water-soluble or oil-soluble radical polymerization initiator is preferable.
As the radical polymerization initiator, a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferable, and when polymerization is performed in an aqueous medium, a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.

In the polymerization of the monomer, a molecular weight modifier may be used. As the molecular weight regulator, aromatic compounds, mercapto alcohols or mercaptans are preferable, and alkyl mercaptans are particularly preferable. Examples of molecular weight modifiers include mercaptoethanol, mercaptoglycerol, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH ₂ = C (Ph) CH ₂ C (CH ₃ ). ₂ Ph, where Ph is a phenyl group.

  The proportions of the monomers (a) to (f) are the same as the proportions of the units based on the monomers (a) to (f), respectively, because the monomers remaining after the polymerization are hardly detected. The preferred embodiment is also the same.

  In the water / oil repellent composition of the present invention, the copolymer is preferably dispersed as particles in a liquid medium. The average particle size of the copolymer is preferably 10 to 1000 nm, more preferably 10 to 500 nm, and particularly preferably 50 to 300 nm. If the average particle diameter is within this range, it is not necessary to use a large amount of a surfactant or the like, the water and oil repellency is good, and no discoloration occurs when dyed fabrics are processed. Among them, the dispersed particles can exist stably and do not settle. The average particle size of the copolymer can be measured by a dynamic light scattering device, an electron microscope or the like.

The solid content concentration of the water / oil repellent composition of the present invention is preferably 25 to 40% by mass immediately after the production of the water / oil repellent composition.
The solid content concentration of the water / oil repellent composition of the present invention is preferably 0.2 to 5% by mass when the article is processed.
The solid content concentration of the water / oil repellent composition is calculated from the mass of the water / oil repellent composition before heating and the mass after drying in a convection dryer at 120 ° C. for 4 hours.

(Mechanism of action)
In the water / oil repellent composition of the present invention described above, in addition to the unit based on the monomer (a) and the unit based on the monomer (b), a unit based on the monomer (c) is further added. In order to obtain an article having good water repellency, oil repellency, washing durability, heavy rain durability, and texture by treating the article with the water / oil repellent composition. be able to.
Further, in the water / oil repellent composition of the present invention, since the copolymer does not have a unit based on a monomer having an R 7 ^F group having 7 or more carbon atoms, an influence on the environment has been pointed out. Perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and precursors and analogs thereof (content when the solid content concentration is 20%) are determined by the method described in International Publication No. 2009/081822. The analytical value of LC-MS / MS can be made below the detection limit.

<Article>
The article of the present invention is an article treated with the water / oil repellent composition of the present invention.
Articles treated with the water / oil repellent composition of the present invention include fibers (natural fibers, synthetic fibers, blended fibers, etc.), textile products, nonwoven fabrics, resin products, paper, leather products, wood, metal products, stone materials, Concrete products, gypsum products, glass products and the like can be mentioned. As the article, a fiber product is particularly preferable.
Examples of the treatment method include a method of applying or impregnating the water / oil repellent composition to the article by a known coating method and then drying.

  When the article is treated with the water / oil repellent composition of the present invention, since the film is flexible, the texture of the fiber product becomes flexible and high quality water / oil repellency can be imparted to the article. Moreover, it is excellent in film adhesion, and can impart water and oil repellency even at low temperature curing. In addition, there is little deterioration in performance due to friction or washing, and the performance at the initial stage of processing can be stably maintained. Moreover, when processed to paper, excellent size, water repellency and oil resistance can be imparted to paper even under low temperature drying conditions. When treated on a resin, glass or metal surface, it is possible to form a water / oil repellent film having good adhesion to the article and excellent film forming properties.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1 to 4 are examples, and examples 5 to 13 are comparative examples.

(Oil repellency)
The test cloth was evaluated for oil repellency according to the test method of AATCC-TM118-1966. The oil repellency was represented by the grade shown in Table 1. A grade marked with + (−) indicates that each property is slightly better (bad).

(Oil-repellent friction durability)
Using a friction tester, the friction surface of the test cloth was rubbed 1000 times and air-dried overnight in a room at a temperature of 25 ° C. and a humidity of 55%, and then the oil repellency of the friction surface of the test cloth was evaluated.

(Water repellency)
The test fabric was evaluated for water repellency according to the spray test of JIS L 1092. The water repellency was expressed in 5 grades of 1-5. The larger the score, the better the water repellency. A grade marked with + (−) indicates that each property is slightly better (bad) than the standard grade.

(Water-repellent washing durability)
For the test cloth, washing was repeated 20 times according to the water washing method of Schedule 103 of JIS L 0217. After washing, it was air-dried overnight in a room at room temperature of 25 ° C. and humidity of 55%, and then the water repellency of the test cloth was evaluated.

(Water repellent friction durability)
Using a friction tester, the friction surface of the test cloth was rubbed 1000 times and air-dried overnight in a room at a temperature of 25 ° C. and a humidity of 55%, and then the water repellency of the friction surface of the test cloth was evaluated.

(Durable torrential rain)
For the test cloth, in accordance with the method described in JIS L 1092 (c) (Bundesmann test), the rainfall amount is 100 cc / min, the rain water temperature is 20 ° C., the rain time is 0 minutes, 5 minutes or 10 minutes. It was rained and water repellency was evaluated. The water repellency was expressed in 5 grades of 1-5. The larger the score, the better the water repellency. A grade marked with + (−) indicates that each property is slightly better (bad).

(Texture)
The test cloth was allowed to stand for one day in a constant temperature and humidity room at room temperature 20 ° C. ± 2 ° C. and humidity 65% ± 2%, and then the flexibility was determined by sensory evaluation according to the following criteria.
○: Soft.
Δ: Normal.
X: Hard.

(Abbreviation)
Monomer (a):
_{C6FMA: C 6 F 13 C 2} H 4 OC (O) C (CH 3) = CH 2.

Monomer (b):
BeA: behenyl acrylate.

Monomer (c):
_{55PET800: CH 2 = C (CH} 3) C (O) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ( manufactured by NOF Corporation, Blemmer (TM) 55PET800 , A≈10, b≈5, [(C ₂ H ₄ O) _a (C ₄ H ₈ O) _b ] number average molecular weight: about 800).

Monomer (d):
VCM: Vinyl chloride.

Monomer (e):
HEMA: 2-hydroxyethyl methacrylate,
HBA: 4-hydroxybutyl acrylate,
NMAM: N-methylolacrylamide.
Monomer (f):
StA: stearyl acrylate,
_{PP800: CH 2 = C (CH} 3) C (O) O- (C 3 H 6 O) c -H ( manufactured by NOF Corporation, Blemmer _{(TM) PP800, c ≒ 13, (} C 3 H 6 O) number average molecular weight of _c : about 754),
_{PME550: CH 2 = C (CH} 3) C (O) O- (C 2 H 4 O) d -CH 3 ( manufactured by NOF Corporation, Blemmer _{(TM) PME550, d ≒ 12, (} C 2 H ₄ O) Number average molecular weight of _d : about 528).

Surfactant s ¹ :
PEO-30: A 10% by mass aqueous solution of polyoxyethylene oleyl ether (manufactured by Kao Corporation, Emulgen (registered trademark) E430, adduct of about 30 mol of ethylene oxide).

Surfactant s ³ :
P204: ethylene oxide propylene oxide polymer (manufactured by NOF Corporation, Pronon (registered trademark) 204, the proportion of ethylene oxide is 40% by mass).

Surfactant s ⁷ :
TMAC: A mixed solution of 63% by mass isopropyl alcohol and water of stearyltrimethylammonium chloride.

Liquid medium:
DPM: Dipropylene glycol monomethyl ether,
Water: Ion exchange water.

Molecular weight regulator:
DoSH: n-dodecyl mercaptan.

Polymerization initiator:
VA061A: 10% by mass aqueous solution of acetate of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA061).

[Example 1]
In a glass beaker, C6FMA 5.60 g, BeA 18.67 g, 55 PET800 0.25 g, PEO-30 7.78 g, TMAC 0.49 g, P204 0.16 g, DPM 18.67 g, water And 0.31 g of DoSH were added and heated at 60 ° C. for 30 minutes, and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho, Biomixer) to obtain a mixed solution.

  The obtained liquid mixture was processed at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 60 ° C. to obtain an emulsion. The obtained emulsion was put into a stainless steel reaction vessel and cooled to 40 ° C. or lower. After adding 3.11 g of VA061A and replacing the gas phase with nitrogen, 6.60 g of VCM was added. While stirring, the polymerization reaction was carried out at 60 ° C. for 15 hours to obtain a copolymer emulsion. Table 2 shows the ratio of units based on each monomer.

  The copolymer emulsion is diluted with distilled water and the solid content concentration is adjusted to 1% by mass, and then a melamine curing agent (DIC, Beccamine (registered trademark) M3) and an acid catalyst (DIC, accelerator). ACX) was added so that each concentration would be 0.3% by mass to obtain a water / oil repellent composition.

  Dyed nylon taffeta or dyed polyester wooly taffeta was dipped in the water / oil repellent composition and squeezed so that the wet pick-up would be 50% by mass and 30% by mass, respectively. This was dried at 110 ° C. for 60 seconds and then dried at 170 ° C. for 60 seconds to obtain a test cloth. The test cloth was evaluated for oil repellency, oil repellency friction durability, water repellency, water repellency washing durability, water repellency friction durability, heavy rain durability and texture. The results are shown in Table 2.

[Examples 2 to 13]
A copolymer emulsion was obtained in the same manner as in Example 1 except that the amount of each monomer charged was changed to the ratio of units based on each monomer shown in Tables 2 to 4. The ratio of units based on each monomer is shown in Tables 2 to 4.
A water / oil repellent composition was obtained in the same manner as in Example 1 except that the emulsion was used. As for Example 13, two kinds of emulsions, Example 5 and Example 12, were mixed at a ratio of 1: 1 as shown in Table 4 to obtain a water / oil repellent composition.
A test cloth was obtained in the same manner as in Example 1 except that the water / oil repellent composition was used. The test cloth was evaluated for oil repellency, oil repellency friction durability, water repellency, water repellency washing durability, water repellency friction durability, heavy rain durability and texture. The results are shown in Tables 2-4.

The water / oil repellent composition of the present invention comprises fiber products (clothing articles (sportswear, coats, blousons, work clothes, uniforms, etc.), bags, industrial materials, etc.), non-woven fabrics, leather products, wood, stones, concretes. It is useful as a water / oil repellent for imparting water / oil repellency to building materials. Moreover, it is useful as a coating agent for filtration materials, a surface protective agent, a coating agent for electronics, and an antifouling coating agent used in the presence of an organic solvent liquid or its vapor. Furthermore, it is also useful for applications where water and oil repellency is imparted by mixing and molding with fiber such as polypropylene and nylon.
In addition, the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2015-106994 filed on May 27, 2015 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (14)

A water / oil repellent composition comprising a copolymer having a unit based on the following monomer (a), a unit based on the following monomer (b), and a unit based on the following monomer (c) and a liquid medium .
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, the group represented by the following Formula (2-1), or the group represented by the following Formula (2-2), Y is fluorine It is a divalent organic group or a single bond having no atom, n is 1 or 2, and X is represented by the following formulas (3-1) to (3-5) when n is 1. Any one of the groups, and when n is 2, any one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C s F 2s + 1 (CH} 2 CF 2) t (CF 2 CF 2) u - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, s is an integer from 1 to 6 T is an integer of 1 to 4, and u is an integer of 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 or more carbon atoms.
Monomer (c): a compound represented by the following formula (5).
^{_{CH 2 = CR 1 C (O}} ) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ··· (5).
However, ^{R 1} is hydrogen atom or a methyl group, a is 3 to 50, b is 1 to 50, the ratio between a and b (a / b) is a 1-3 . _The binding order of the (C _{2 H} 4 O) units and _{(C 4 H} 8 O) units is not limited.   The content ratio of the units based on the monomer (a) is 5 to 40% by mass with respect to the units based on all monomers constituting the copolymer, and is based on the monomer (b). The water / oil repellent composition according to claim 1, wherein the unit content is 40 to 94.9% by mass, and the unit content based on the monomer (c) is 0.1 to 20% by mass. object. The water / oil repellent composition according to claim 1 or 2, wherein the copolymer further comprises units based on the following monomer (d).
Monomer (d): Halogenated olefin.   The water / oil repellent composition according to claim 3, wherein the monomer (d) is vinyl chloride.   5. The water-repellent / repellent property according to claim 3, wherein the proportion of the units based on the monomer (d) is 30% by mass or less with respect to the units based on all monomers constituting the copolymer. Oil composition. The water / oil repellent composition according to any one of claims 1 to 5, wherein the copolymer further has a unit based on the following monomer (e).
Monomer (e): A monomer having a functional group capable of crosslinking.   The water / oil repellent composition according to any one of claims 1 to 6, wherein the liquid medium is an aqueous medium. In the presence of a surfactant and a polymerization initiator, a monomer component containing the following monomer (a), the following monomer (b) and the following monomer (c) is polymerized in a liquid medium, A method for producing a water / oil repellent composition, which is a copolymer.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, the group represented by the following Formula (2-1), or the group represented by the following Formula (2-2), Y is fluorine It is a divalent organic group or a single bond having no atom, n is 1 or 2, and X is represented by the following formulas (3-1) to (3-5) when n is 1. Any one of the groups, and when n is 2, any one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C s F 2s + 1 (CH} 2 CF 2) t (CF 2 CF 2) u - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, s is an integer from 1 to 6 T is an integer of 1 to 4, and u is an integer of 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 or more carbon atoms.
Monomer (c): a compound represented by the following formula (5).
^{_{CH 2 = CR 1 C (O}} ) O - [(C 2 H 4 O) a (C 4 H 8 O) b] -H ··· (5).
However, ^{R 1} is hydrogen atom or a methyl group, a is 3 to 50, b is 1 to 50, the ratio between a and b (a / b) is a 1-3 . _The binding order of the (C _{2 H} 4 O) units and _{(C 4 H} 8 O) units is not limited.   The proportion of the monomer (a) is 5 to 40% by mass, the proportion of the monomer (b) is 40 to 94.9% by mass with respect to the total amount of the monomer components, The method for producing a water / oil repellent composition according to claim 8, wherein the proportion of the monomer (c) is 0.1 to 20% by mass. The method for producing a water / oil repellent composition according to claim 8 or 9, wherein the monomer component further comprises the following monomer (d).
Monomer (d): Halogenated olefin. The method for producing a water / oil repellent composition according to any one of claims 8 to 10, wherein the monomer component further comprises the following monomer (e).
Monomer (e): A monomer having a functional group capable of crosslinking.   The method for producing a water / oil repellent composition according to any one of claims 8 to 11, wherein the liquid medium is an aqueous medium.   An article treated with the water / oil repellent composition according to any one of claims 1 to 7.   The article of claim 13, wherein the article is a textile product.